DE2744316A1 - ANIONIC, ARALIPHATIC COMPOUNDS - Google Patents

Description

CIBA-GEIGY AG, CH-4002 Basel OIlJ / "* ^ VJjL-LvJi S

Case 1-10726 / 1 + 2 / + *

GERMANY

Anionic, araliphatic compounds

The present invention relates to anionic araliphatic compounds, a process for their preparation and their use as a dyeing aid in dyeing synthetic polyamide fiber material with anionic dyes.

The inventive, anionic, araliphatic Compounds correspond to the general formula

Z Z

I ¹ I ²

(1) RAO <CH-CH-O) ~ ^ -_- ₁ CH ₂ -CH-CH ₂ -OX SO ₃ M OSO ₃ M

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A is a mononuclear or binuclear aromatic radical, R alkyl with 4 to 22 carbon atoms, X alkyl with 1 to 18 carbon atoms,

from Z ₁ and Z _? one is hydrogen and the other is hydrogen or methyl,

M is a cation and η is 1 to 21.

Λ means: preferably a benzene, naphthalene or diphenyl radical which is optionally further substituted. As a substituent e.g. hydroxyl, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms or halogens, such as chlorine. A preferably represents a benzene radical which continues with hydroxyl, chlorine, methyl or methoxy can be substituted. In particular, A denotes an unsubstituted benzene radical.

The alkyl substituents R and X can be straight-chain or branched. Examples of alkyl radicals are η-butyl, sck. 3utyl, tort.-butyl, amyl, tert.-pentyl, n-hexyl, ii-cctyl, tert-octyl, 2-ethyl hexyl, nonyl, decyl, dodecyl, Pentadccy1 and Octadecyl. X can also be methyl, ethyl, n-propyl or isopropyl while R can also be eicosyl or docosyl dars tellc-n.

Z ^ is preferably hydrogen, while Z _? Can mean hydrogen or methyl. In particular, Z ₁ and both are hydrogen.

As a cation, M can, for example, be hydrogen Alkali metal, especially sodium or potassium, an alkaline earth metal, especially magnesium or calcium or an Aüjr.oniuirgruppe represent. The term "Arnnioniuriigruppe" as used herein refers both to ar ^ onium (KH,), and to substituted ammonium groups.

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27AA316

The latter are derived e.g. from aliphatic amines such as di- or triethylamine or mono-, di- or triethanolamine, cycloaliphatic amines, such as cyclohexylamine or heterocyclic Amines ν; ie piperidine, morpholine or pyridine. M is preferably hydrogen, an alkali metal or ammonium, η is expediently 1 to 6, preferably 1 to 3 and in particular 1.

Practically important anionic araliphatic compounds according to the present invention correspond to the general formula

Z ₁ Z _n

/ - \ Il

wherein

R, alkyl with 4 to 18 carbon atoms, preferably 9 to 12 carbon atoms,

of Z-, and Z _{n of} one hydrogen and the other hydrogen or methyl, preferably both hydrogen,

X. Alkyl of 1 to 8 carbon atoms, preferably 4 to £ Carbon atoms,

M, hydrogen, alkali metal or an ammonium group and n is 1 to 6, preferably 1 to 3.

Here, M, especially sodium or potassium as an alkali metal and especially ammonium as an amnonium group, is ore the Trimethy lan.monium-, MonoathanolarT.oni.ur .. ··, DiSthanoiammoniv .-- or Triäthanolau: n.: oniunigruppe.

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Anionic ones are of particular interest araliphatic compounds of the general formula

on μ ² OSO, .M ₉

S0_M ₉ . 6 2

R ₂ alkyl of 9 to 12 carbon atoms

X ₉ alkyl of 4 to 8 carbon atoms

M ₉ hydrogen, alkali metal or ammonium and

Π2 is 1 to 3, preferably 1.

The anionic araliphatic ones according to the invention Compounds are made by having an araliphatic Compound of the general formula

Z ₁ Z ₂ OH

in which A, R, X, Z-,, Z ₉ and η have the meaning given. treated with a sulfonating agent and optionally converted the sulfonation product into a salt.

The compounds of the formula (4) required as starting materials are earthed, for example, by reacting a compound of formula

(5) R-A-O-C-CH-CIi-O ^ yH

^Z l K

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where A, R, Z, and Z _? and η have the meaning given with a glycidyl ether compound of the formula

(6) qH ₉ -CH-CH ₂ -OX

wherein X has the meaning given, prepared.

This reaction is preferably carried out in the presence of an acidic or alkaline catalyst such as sodium, Potassium, sodium or potassium hydroxide, sodium or potassium methylate or boron trifluoroetherate.

The inventive treatment of the starting materials of the formula (4) with the sulfonating agents is expediently carried out by customary methods, for example with conc. Sulfuric acid, Schv.'efeltrioxyd, oleum or preferably chlorosulfonic acid. It is advantageously carried out in a solvent which is inert under the reaction conditions. Examples of suitable solvents are chlorinated hydrocarbons such as chloroform, carbon tetrachloride, ethylene chloride, methylene chloride, trichlorethylene, trichloroethane, but preferably ethyl acetate, dimethyl methane phosphonate or diethylene glycol diethyl ether. The temperature range for the sulfonation is suitably between 5 to 100 ° C, preferably between 50 and 70 ⁰ C. The resulting free acids can then be converted into the corresponding alkali metal or ammonium salts. The conversion into the salts takes place in the usual way by adding bases such as ammonia, monoethanolamine, triethanolamine or, preferably, alkali metal hydroxides such as sodium or potassium hydroxide at room temperature (20-3O ° C.). In this way, one can obtain aqueous preparations which contain, for example, 25 to 40% of sulfonation product.

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Depending on the size of the radicals R and X and depending on Under working conditions, cloudy preparations can be obtained, which, however, turn into clear solutions when diluted with water. You can also leave any cloudy preparations by adding a Solubilizers, such as urea in particular, are converted into clear products.

The new anionic araliphatic compounds are used as dyeing auxiliaries, in particular as leveling agents when dyeing or printing synthetic polyamide fiber material with anionic dyes. Suitable fiber materials are those made from adipic acid and hexamethylenediamine (polyamide 6,6), from i. -Caprolactan (polyamide 6), from (m- aminoundccanoic acid (polyamide 11), from k'-aminoenanthic acid (polyamide 7), from & - aminopelargonic acid (polyamide 8) or from sebacic acid and hexamethylenediamine (polyamide 6,10). The polyamide -Fiber materials can also be used as mixed fabrics with one another or with other fibers, for example mixtures of polyamide / wool or polyamide / polyester.

The fiber material can be in various processing stages exist, e.g. in the form of flakes, knitted fabrics such as knitted or knitted fabrics, yarn bundles, bobbins, as nonwovens or preferably as woven fabrics.

The anionic dyes are, for example, salts of metal-free or heavy metal-containing mono-, dis- or polyazo dyes, including the formazan dyes and the anthraquinone, xanthene, nitro, triphenymethane, naphthoquinonine, and phthalocyanine dyes. The 1: 1 and 1: 2 metal complex dyes are also of interest. The anionic character of this color Collie can be formed by metal complex formation alone and / or by r.aura, sal '<

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Substituents such as carbic acid groups, sulfuric acid or phosphonic acid ester groups, phosphonic acid groups or sulphonic acid groups. These dyes can in the molecule also so-called reactive groups, which with enter into a covalent bond with the polyamide to be dyed. The so-called acidic dyes are preferred.

The amount of dyes added to the liquor depends on the desired color strength, in general Quantities of 0.1 to 10 percent by weight, based on the fiber material used, have proven useful.

The dye baths can contain mineral acids such as sulfuric acid or phosphoric acid, organic acids, advantageously lower, aliphatic carboxylic acids such as formic, acetic or Oxalic acid and / or salts, such as ammonium acetate, ammonium sulfate or preferably contain sodium acetate. The acids are used primarily to adjust the pH of the invention liquors used, which are usually 3.5 to 6.5, preferably 4 to 6 is.

The dye baths can also contain the usual electrolytes, dispersants, antifoams and wetting agents.

• ·

The dyeings are advantageously carried out using an aqueous liquor using the exhaust process. The liquor ratio can accordingly be chosen within a wide range, for example 1: 1 to 1: 100, preferably 1:10 to 1:50. The amounts used in which the new anionic araliphatic compounds are added to the dye baths range from 0.5 to 10 percent by weight, preferably 1 to 3 percent by weight, based on the weight of the material to be dyed. The dyeing is expediently carried out at a temperature in the range from 75.degree. C. to the boiling point and preferably at a temperature from 90 to 98.degree. 809815 / 06B1

The textile material is preferably introduced into a liquor which has a temperature of 40 to 50 ° C. and the material is treated at this temperature for 5 to 15 minutes. Then you are the dyes at 40 to 60 ⁰ C and increases to slow the temperature of the liquor to dye at boiling temperature 20 to 90 vorzugsv7ei.se 30 to 60 minutes. At the end the dye liquor is cooled and the dyed material is rinsed and dried as usual.

The dyeing of the synthetic polyamide fiber material can also be carried out by a printing or padding process. Here, the optionally thickened printing paste or liquor containing dye, contains according to the invention anior.ische ^ araliphatic compound, acid, and possibly 'further additives, printed on the fiber or padded, preferably at a temperature between 10 ⁰ C and 40 ° C. The padded or printed fiber material is then subjected to a heat treatment, such as steaming, preferably at temperatures of 98 to 105 ° C. and superatraospheric pressure, expediently for 10 to 30 minutes.

The new anionic araliphatic compounds are valuable dyeing auxiliaries for dyeing synthetic materials Polyamide fiber material. You can use these materials: dye evenly with anionic dyes, especially with the so-called acidic dyes, avoiding dr.s. streaky dyeing due to the material, especially with polyane fiber mixtures and tissue occurs.

Further advantages are the low foaming of the dyebaths, which make the inventive products anionic Contain araliphatic compounds, furthermore the good water solubility and the good compatibility with other ir.i Ftbath existing substances, so that it does not increase when dyeing at higher temperatures and over a longer period of time

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Fillings and unwanted deposits on the Fiber material comes. The products according to the invention work stabilizing on the paintwork, so that it remains during the entire dyeing process have their full effectiveness.

In the following examples, percentages are percentages by weight and parts are parts by weight.

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example 1

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a) 220 g of p-nonylphenol are ^{stirred with 2 g of sodium hydroxide powder at 60-7O 0} C for 1 hour. It can be: one g of butyl glycidyl ether over 45 minutes 140 r.iit an epoxy equivalent weight of 137 g zutrepfen, heated at an outside temperature of 120 ⁰ C and maintained for 3 hours at this Auüsentemperatur. The internal temperature temporarily rises to 145 ° C. Subsequently, the Reaktionsgernisch is held for 1 to 3 hours at 15O-16O ^C C to terminate the reaction.

b) In a round-bottomed flask, 144 g of gas a) are prepared. Zv? Ischenproduktes and 30 g Essigester for 2 hours at 60 ⁰ C. 106 g of chlorosulfonic acid is added dropwise. Then holding the SuIfonierungsg? Uiisch still V7eitere uv? Ei hours at 60 ⁰ C. Thereupon, the Heaktionsgemisch is added within 3 hours at 2O-25 ° C to a mixture of 163 g of 30% sodium hydroxide and 120 g of water, the vjobei The pH value of the solution should not drop from 7-9 with the additional addition of sodium hydroxide solution. The reaction product obtained is then brought to an enci weight of 630 g with water, a clear solution being obtained which contains about 35% of the sulfonation product of the formula

(11) C ₀ H ₁₀ - /, \> od ^ -cH-cH ^ -o-c ^ H ^

CH-CH OSO ^ Na

contains. Fine 0.0l7oige solution has (based on active substance) at 20 ⁰ C a surface tension of 39.7 dyn / cm.

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Example 2

a) 308 g of an adduct of 1 hol of p-nonyphenol and 2 mol of aefchyienoxid are stirred with 2 g of sodium hydroxide powder at 60-7O ⁰ C for 1 hour. It is allowed to over 45 minutes 140 g ButylglycidylUther with a EpoxyKquiva-Ientgev7icht of 137 g is added dropwise, warmed to an external temperature of 120 ⁰ C and maintained for 3 hours at this Aussentcmperatur. The internal temperature temporarily rises to 132 ° C. Subsequently, the reaction mixture is maintained for 1 to 3 hours at 150-160 ⁰ C to terminate the reaction

b) In a round bottom flask to be 179.2 g of geir.Mss a) intermediate prepared 30 g Essigester wa'hrend 2 hours at 60 ⁰ C, 106 g of chlorosulfonic acid is added dropwise. The sulfonation product obtained is added in the same way as described in Example Ib) to 163 g of 30% sodium hydroxide solution and 120 g of water. The solution obtained is then brought to a final weight of 724 g with water. A clear solution is obtained which contains about 35% of the sulfonation product of the formula

contains. Surface tension at 20 ° C of 37.5 dynes / cm, measured on a 0.01% solution (based on the active substance).

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Example 3

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a) 256 g of p-dodecylphenol are stirred for 1 hour at 60-7O ⁰ C ir.it 2 g Natriumhydroxydpulver. It is initiated within 45 minutes of 108 g Aethylglycidyläther ir.it a Epoxyäqui- · valentgev; layer of 105 g is added dropwise, heated to a Aussenteraperatur of 120 ⁰ C and maintained for 3 hours at this temperature. Me inner temperature rises temporarily to 150 ⁰ C. Then the reaction is complete, the reaction mixture is held for 1 to 3 hours at 150-16O ⁰ C.

b) In a round-bottomed flask, 145.6 g of the according to e) produced intermediate and 30 g of ethyl acetate allowed to drop 106 g of chlorosulfonic acid over 2 hours at 60 ° C. The sulfonation mixture obtained is described in the same manner as in Example Ib) to give 163 g of 30% strength sodium hydroxide solution and 120 g of water are added. The solution obtained is then brought to a final weight of 632 g with water. Man receives a clear solution that contains about 35% of the sulfonation product: the formula

OSC ₅ Na
3

contains. Surface tension at 20 ^° C. of 40.7 dynes / cm, measured on a 0.01% solution (based on the active substance).

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Example 4

a) 150 g p-tert. Butylphenol are stirred with: 2 g of sodium hydroxide powder for 1 hour at 60-70 ° C. On it leaves
140 g of B \ ityl glycidyl ether of
add dropwise to an epoxy equivalent weight of 137 g, heated
to an outside temperature of 120 ⁰ C and holds 3 hours at this outside temperature: ur. The internal temperature temporarily rises to 136 ° C. Then, for completion of the reaction, the reaction mixture is held for 1 to 3 hours at 150-16O ⁰ C.

b) In a round bottom flask, 116 g of the according to a) produced intermediate and 30 g of ethyl acetate allowed dropwise 106 g of chlorosulfonic acid at 6C ° C over 2 hours. The sulfonation mixture obtained is in the same way as described in Example Ib) to 163 g of 30% sodium hydroxide solution and 120 g of water are added. The solution obtained is then brought to a final weight of 602 g with water. Man receives a clear solution that contains about 30% sulfonation product the formula

(14) CH ₃ - |: - ^^^ - O-CH ₂ -CH-CK ₂ -OC ₄ H ₅

3 SO ₃ Na

contains. A 12:01% solution (based on active substance) has a surface tension of 54.5 dyn / cra at 20 ⁰ C.

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Example 5

a) 220 g of p-nonylphenol are stirred with 2 g of Katriuriihydroxydpulver for 1 hour at 60-70 ° C. It is allowed a period of 45 minutes, 200 g of 2-Aethylhexylglycidyläther of an epoxy equivalent weight of 198 g is added dropwise, warmed to an external temperature of 120 ⁰ C and maintained for 3 hours at this outside temperature. The internal temperature temporarily rises to 133 ° C. The reaction device is then kept at 150-160 ° C for a further 1 to 3 hours to end the reaction.

b) In a round-bottomed flask to 168 g of the geiYiaus a) intermediate prepared Esr.igester 30 g for 2 hours at 60 ⁰ C, 106 g of chlorosulfonic acid is added dropwise. The sulfonation mixture obtained is added in the same way as described in Example Ib) to 163 g of 30% strength sodium hydroxide solution and 120 g of water. The product obtained is then adjusted to a final weight of 684 g with water. A cloudy, viscous preparation is obtained which dissolves well in water and contains about 35% of the sulfonation product of the formula

(15) C ₉ H ₁₉ - / ι \ -O-CH ₂ -CH-CH ₂ -O-CH ₂ -CtH (ClI ₂ ) 3Cl ₃

SO ₃ Na ^0S0 3 ^{Na C} 2 ^H 5

contains. Surface tension at 20 ° C of 35.7 dynes / cm, measured on a 0.01% solution (based on the active substance).

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Example 6

a) 304 g of n-pentadecylphenol are heated with 2 g of sodium hydroxide powder at 60-7O ⁰ C for 1 hour. It is allowed within 45 minutes 126 g Isopropylglycidyläther with an epoxy equivalent weight of 123 g is added dropwise, heated to a Aussenteinperatur of 120 ⁰ C and maintained for 3 hours at this Aussentemptrratur. The internal temperature temporarily rises to 128 ° C. Subsequently, the reaction mixture is maintained for 1 to 3 hours at 150-16O ⁰ C to terminate the reaction.

b) In a round-bottomed flask to 172 g of getnäss a) intermediate prepared Essigester 30 g for 2 hours at 60 ⁰ C, 106 g of chlorosulfonic acid is added dropwise. The sulfonation mixture obtained is added in the same way as described in Example Ib) to 163 g of 30% strength sodium hydroxide solution and 120 g of water. The product obtained is then brought to a final weight of 653 g with water. A cloudy, viscous preparation is obtained which dissolves well in water and contains about 35% of the sulfonation product of the formula

(16) ^η ~ ° 15 ^Η 3ΐΛ / / -0 "CH ₂ -CH-CH ₂ -O-CH (CH ₃ )

<j> ^S0 3 ^Well

contains. Surface tension at 20 ° C of 51.1 dynes / cm, measured on a 0.01% solution (based on the active substance).

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Example 7

a) 206 β p-tert-octylphenol are stirred with 2 g of sodium hydroxide powder at 60-70 ° C. for 1 hour. It is allowed within 45 minutes 140 g Butylglycidylatber with a Epoxyaquivalentgev-eight of 137 g zutropfcn heated to a Aussenterrperatur of 120 ⁰ C and 3 hours at this h'alt Aussenteroperatur. The internal temperature rises temporarily to 125 ° C. The reaction mixture is then maintained V7ird 1 to terminate the reaction to 3 hours at 150-16O ⁰ C.

b) In a round bottom flask, 138.4 g of geiiüiss a) intermediate prepared Essigester 30 g for 2 hours at 60 ⁰ C, 106 g of chlorosulfonic acid is added dropwise. The sulfonation mixture obtained is added in the same manner as described in Example Ib) to 163 g of 30% strength Netri.umhydroxydlösung and 120 g of water. The solution obtained is then made up to a final weight of 596 g with water. A clear solution is obtained which contains about 35% of sulfonation product of the formula

(17) tert-octyl

SO ₃ Ka OSO ₃ Na

contains. Surface tension at 20 ⁰ C of 42.4 dyn / cni measured ah a 0.01% strength Lccung (based on active substance).

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Example 8

a) 220 g of p-nonylphenol with 2 g gerlihrt Natriumhydroxydpulver 1 hour at 60-7O ⁰ C. 100 g of methyl glycidyl ether with an epoxy equivalent weight of 98 g are then added dropwise over a period of 45 minutes, and the mixture is heated; to an outside temperature of 120 ° C and hold for 3 hours at this outside temperature. The internal temperature temporarily rises to 136 ° C. ^{The reaction mixture is then kept at 150-1GO 0} C for a further 1 to 3 hours to end the reaction.

b) In a round bottom flask, 128 g of the according to a)
produced intermediate and 30 g of ethyl acetate during

2 hours at 60 ⁰ C, 106 g of chlorosulfonic acid is added dropwise. The sulfonation mixture obtained is added in the same way as described in Example Ib) to 163 g of 30% strength sodium hydroxide solution and 120 g of water. The solution obtained is then brought to a final weight of 547 g with water. A clear solution is obtained which contains about 35% of the sulfonation product of the formula

(18) C ₉ H ₁₉ - ^ I Vo-CH ₂ -CH-CH ₂ -O-CH ₃

SO ₃ N ₃ ^ÖS0 3 ^Na

contains. Surface tension at 20 ^° C. of 38.4 dynes / cm, measured on a 0.01% solution (based on active substance).

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Example 9

72 g of the intermediate product prepared according to Example 3 and 50 ml of methylone chloride are placed in a round bottom flask. 49 g of chlorosulfonic acid are then allowed to drop in at 5 ° C. over the course of one hour. The SuIfonierungsgemisch is then stirred for 1 hour at I) -IO ⁰ C and for 3 hours at 2O-3O ° C. It is then heated to 60 ° C, whereupon the head is distilled off in methyl chloride. Then ncuuralisic-rt irs.r the reaction product ir.it 27 g monoethanoiamine, v; obei ein? y.'dVie mass is created, which is dissolved by adding 120 g of water. The product obtained is filtered, boiled and adjusted to a final weight of 547 g with L'asser. A clear solution is obtained which contains about 30% of the sulfonation product of the formula

(19) C ₉ H ₁₉ - / ζ VO-CH ₂ -CH-CH ₂ -OC ₄ H ₉

contains. Surface tension at 20 ^° C. of 42.3 dynes / cn: measured on a 0.01% solution (based on active substance).

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Example 10

In a ttundkolben of gerab'ss example la) are added to 144 g of the intermediate prepared Essigester 30 g for 2 hours at 60 ⁰ C. 94 g of chlorosulfonic acid left zutropfcn. The sulfonation obtained is added in a manner similar to that described in Example Ib) to 147 g of 30% strength sodium hydroxide solution and 120 g of water, a cloudy product being obtained. This is adjusted to a pH value of 5 with acetic acid and 60 g of urea are added, whereupon a clear solution is obtained which is adjusted to a final weight of 630 g with water. The clear solution obtained contains about 35% of sulfonation product. A 0.01% solution (based on the active substance) has a surface tension at 20 ^° C. of 41.6 dynes / cm.

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Example 11

a) 220 g nonyl phenol and 2 g of sodium methylate are heated to 140 ⁰ C. 140 g of butyl glycidyl ether with a Epoxyaequivaler.tgewicht of 137 GM / ground in one hour at an external temperature of 140 ⁰ C is added dropwise, keeping the internal temperature rises to about 150 ⁰ C. Stirring is continued for one hour at an external temperature of door 140 ⁰ C and then held for 40 Hinuten at 155-16O ° C.

b) In a round-bottomed flask to 144 g of the gernäss a) intermediate prepared 40 g Dimethylmethanphosphonnt for 1-2 hours 94 g of chlorosulfonic acid is added dropwise Then holding the Sulfierungsgemisch further two hours at 60 ⁰ C. The SuIfierungsprodukt obtained is then in 3 hours at 20-25 ° C. to a mixture of 120 g of 30% ammonia and 155 g of water. The solution obtained, which has a pH of about 8, is then adjusted to a final weight of 630 g with water. A clear solution is obtained which contains about 35 % of the compound of the formula

(20) ^C 9 ^H 19 "^ 3 ~ °° ^Η 2Ϊ ^Η ° ^Η 2 ⁰⁰ 4 ^Η 9

SO ₃ NH ₄

contains. Surface tension at 20 ° C of 39.7 dynes / cm, measured on an O.017oigen solution (based on active substance).

Example 12

a) 220 g of the adduct of 1 mole of nonylphenol and 5 moles of ethylene oxide and 1 g Natriuruir.ethylat are heated to 140 ⁰ C. 70 g of butyl glycidyl ether with an epoxy equivalent weight of 137 g are added dropwise in one hour at an outside temperature of 1 - ': 0 ° C: .. It is stirred for one hour at 140 ⁰ C and then another 2-3 hours at 155-16O ° C held.

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b) In a Rundkolbcn intermediate product prepared to 116 g of according ei) 20 g Diaethylenglycoldiaethyläther V7ährend are allowed one hour 53 g of chlorosulfonic acid at 60 ⁰ C zuLropfen and holds a further 2 hours at 60 ° C. The reaction product obtained is then added in 3 hours at 20-25 ° C. to a mixture of 60 g of 30% ammonia and 80 g of water. The solution obtained, which has a pH of about 8, is then adjusted to a final weight of 436 g with water. The following is obtained: a clear solution which contains about 35% of the compound of the formula

(21) C ₉ II ₃ 9-

- O (CH ₂ CH ₂ O) ₅ -OCH ₂ Cl

OSO ₀ NH. 3 4

SO ₃ NH ₄

contains. Surface tension of the joint at 20 ° C of 36.5 dyn / cin, measured on an O.O3T4igen solution (based on Active substance).

Example 13

a) 308 g of the adduct of 1 mole of nonylphenol and 9MdL Aelhylencxic and 2 g sodium methyl are heated to at 140 C ^c. 70 g of butyl glycidyl ether. an epoxy equivalent weight of 137 g are allowed to drop in at an outside temperature of 140 ° C. in one hour. It is continued for one hour at 140 ° C and then held at 155-16O ° C for another 2-3 hours.

b) In a round bottom flask to be 151.2 g of geinäss a) intermediate and produced 20 g Diaethylenglycoldiaethyläther during lh hours at 6O ⁰ C is added dropwise 53 g of chlorosulfonic acid. One holds the SuI f 5. e rung ε Roman further

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2 hours at 6O ⁰ C. The Unisefczungsprodukt is then in

Added 3 hours at 20-25 ° C to a mixture of 60 g aramonia 30 % and 80 g water. The solution obtained, which has a pH of 8, is then brought to a final weight of 542 g with water / water. A clear solution is obtained which contains about 35 % of the compound of the formula

(22) C ₉ H _ig ^^ - 0 (CH ₂ CH ₂ O) ₉ -CH ₂ -CH CH ₂ -OC ₄ H ₉

! θ, NH,

OSO ₃ Ml ₄

contains. Surface tension of the compound at 20 ⁰ C of 42.3 dyn / cm, measured on a 0.017oigen solution (based on active substance).

Example 14

a) 275 g of the adduct of 1 mole of nonylphenol and 20 moles of ethylene oxide and 2 g of sodium methylate are erv to 140 ^c C / ärmt. 35 g Butylglydicyläther be g of an epoxy equivalent weight of 137 is added dropwise in one hour at an external temperature of 140 ⁰ C. It is weitergerUhrt one hour at 140 ⁰ C and held still for 2-3 hours at 155-16O ° C.

b) In a round-bottomed flask to 124 g of the geniäss a) intermediate and produced 30 g Diaethylenglycoldiaethyläther for 1 hour 27 g of chlorosulfonic acid at 60 ° C is added dropwise and then another 2 hours at 6O ⁰ C is still held. The reaction product is g in 3 hours at 20-25 ⁰ C to a mixture of 30 ammonia 30% and 80 g water were added. The solution obtained, which has a pH of 8, is adjusted to a final weight of 406 g with water. A clear solution is obtained which contains about 35% of the compound of the formula

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(23) ^C 9 ^H 19 "<J" 0 (CH ₂ CH ₂ O) ₂₀ CII ₂ -CH

OSO ₃ NH ₄

SO ₃ NH ₄

contains. Surface tension of the compound at 2O ⁰ C of 42.5 dyn / cm, measured at a 0.01% solution, based on active substance.

Example 15

a) 55, 6 g of the adduct of 1 mol of nonylphenol and 1 mol propylene oxide and 0, 5 g of sodium methoxide are heated to 140 ⁰ C, followed by one hour 28 g in butyl glycidyl ether with an epoxy equivalent weight of 137 g added. The temperature rises temporarily to 145 ⁰ C. Then the reaction mixture for 2 hours at 140 ° C and 2 hours at 150 - 160 ⁰ C held outside temperature.

b) In a round-bottomed flask 62.7 g of according to a) intermediate prepared Diäthylenglycoldiäthyläther 15 g for 1 to 2 hours 36 g of chlorosulfonic acid at 6O ⁰ C is added dropwise. The sulfonation mixture is then added in 3 hours at 20-25 ° C. to a mixture of 45 g of 30% ammonia and 60 g of water, whereupon the resulting solution is adjusted to a final weight of 244 g with water. A clear solution is obtained with a pH of 8-9, which is about 35% of the compound of the formula

(24) C ₉ H ₁₉ ~ / V-OCH ₂ -CH-OCH ₂ -CHCh ₂ -OC ₄ H ₉

CH ₃ OSO ₃ NH ₄

SO ₃ NH ₄

contains. The surface tension of a solution O.OlXigen, based on active substance, at 20 ⁰ C is 34.8 dynes / cm.

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Example 16

a) 45.8 g To Hexylnaphthol and 0.45 g of sodium methylate are at 140 ⁰ C 28 g Butylglycidylälher with an epoxy equivalent weight of 137 g in one hour was added, the temperature temporarily rises to 155 ° C. It, keeping the outer temperature for 2 hours at 140 ⁰ C and then for 2 hours at 150-160 ° C.

b) In a round-bottomed flask 55.3 g of according to a) intermediate prepared 36 g of chlorosulfonic acid at 60 ⁰ C is added dropwise in 2 hours, followed by holding for 2 hours at 60 ⁰ C the mixture. The sulfating mixture is then added in 3 hours at 20-25 ° C. to a mixture of 45 g ammonia 307oig and 60 g v / a, whereupon the resulting solution is adjusted to a final weight of 218 g with water. A clear solution is obtained which contains about 35% of the compound of the formula

^C 6 ^H 13

OCH ;; - CH - CH
OSO ₃ NH ₄

C ₄ H ₉

contains.

SO ₃ NH ₄

The surface tension of a 0.017 _o solution, based on active substance, at 20 ⁰ C is 38.9 dynes / cm.

80981 5/0651

2? 27U316

Example 17

a) To 33 g of nonylphenol and 0.35 g of sodium methylate are at 140 ⁰ C in one hour 39.8 g Dodecylglycidylather with an epoxy equivalent weight of 265 g is added dropwise, keeping the temperature temporarily rises to 151 ^C C. The exterior temperature, then holding for 2 hours at 140 ^c C and 2 hours at 150-160 ⁰ C.

b) In a round bottom flask is allowed to 48.5 g of according to a) intermediate prepared Diäthylenglycoldiäthyläther 20 g 24 g of chlorosulfonic acid are added dropwise and the mixture is kept for 2 hours at 60 ⁰ C. The SuIfierungsgemisch it is at 20 - 25 ° C for 3 hours to a mixture of 30 g of ammonia 307 _o ig and 40 g of water is added dropwise, whereupon the resulting solution is adjusted with water to a final weight of 181 g. A thin paste is obtained with a pH of 8-9, which is about 35% of the compound of the formula

OSO ₃ NH ₄

SO ₃ NH ₄

contains. The surface tension of a 0.01% solution, based on the active substance, at 20 ^° C. is 38.4 dynes / cm.

80981 5/0651

Example 18

a) 24.2 g of konylphenol and 0.25 g of sodium niethylate are heated to 60 ° C. and 41.8 g of stearylglycidyl ether with an epoxy equivalent weight of 377 g are added. Then the mixture is heated slowly to 140 ^c C, holding it for 2 hours at this temperature and 2 hours at 150-160 ⁰ C.

b) In a round bottom flask is allowed to 60 g of according to a) intermediate product, and 20 g Diäthylenglycoldiäthylather at 60 ⁰ C for 1-2 hours 24 g of chlorosulfonic acid are added dropwise and the temperature is maintained for 2 hours at 60 ⁰ C. The suif ierunp.sgemisch is then added at 20-25 ° C. to a mixture of 30 g of 30% ammonia and 40 g of water over a period of 3 hours, after which the solution is brought to a final weight of 202 g with water. A product is obtained which contains about 35% of the compound of the formula

(27) C ₉ H ₁₉ - / V 0 - CH ₂ - CH - CH ₂

- CH ₂ O

OSO ₀ NH, 3 4

SO ₀ NH,
3 4

contains. The surface tension of a 0.017 _o solution, based on active substance, at 20 ° C is 47.9 dynes / cm.

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- 2/1

Example 19

10 g of a streaky-colored knitted fabric made of polyamide 6.6 are 10 minutes, in 400 ml of a liquor containing 0.8 g of Mononatriur.iphosphr. i ~. ict v.'orden placed and 0.2 g Dinatriuniphosphnt on τη) C and containing 0.1 £ of rremass Example 2 aqueous preparation prepared, treated at 40 ⁰ C.
On this counts n;?. N 0.03 g of a dissolved commercially available; Dye of the formula

(101)

Uli O

0.03 g of a dissolved commercial dye of the formula

(102)

809815/0651 ORIGINAL BATHROOM

3Ί

and moves to the knitted fabric at for 10 minutes. '' lO '-' C. i>;: oach the dye liquor is heated; to boiling point within 30 minutes: temperature and color 60 minutes at this temperature. N ;. eh der.-, cooling, the float ο the colored VM rkware r.iit V ';-) rr; or rinsed and dried. A streak-free, level £ jvUne coloring is obtained n: it r: iii: cn Eel ·, thru ten.

Instead of the PriiparaLes sufficient. ^ R. Example 2 köi'-ien with 'similar g \' it (? n results ηυοίι die w ^ sseri gen Fräp ^ r.'jte gcn'ass the case of i-plo'i en 1 and 3 to 18 can be used.

Example 20

Earth 100 g of a streaky-colored knitted fabric made of polyamide 6.6 in 4000 ml of a liquor containing 3.0 g of Animonr.eeI: r: t and `` .si'ig-Eüure Has been adjusted to pH 5 uncj 2 g of the gem'ass example 5 prepared aqueous preparation contains, introduced. With constant movement of the textile material you raise the Bath temperature to 98 ° C. within 25 minutes. Then r.ir.n 0.5 g of a dissolved commercial dye remotely!

and colors at 60 minutes. Boiled, n ^ rature. ] \ Y.ch the AM; ühlen of the liquor is the colored V. ^T are rinsed with water and dried. A level, streak-free, brilliant violet dyeing iv. With good fastness properties is obtained.

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BATH ORIGINAL

- *> - 27U316

Example 21

In a bath that reveals 0.4 g of the preparation prepared in accordance with Example 1 dissolved in 800 ml of water: and adjusted to pH 4 with 0.6 g of ammonium acetate and acetic acid, 20 g of a streaky-tinting knitted fabric made of polyamide 6.6 for 10 minutes at 40 ⁰ C treated. Now set to 0.1 g of a dissolved dye represented by the formula Example 20 (103} and rllhrt further 10 Minuteri at 40 ⁰ C. Then the bath temperature was increased in 30 minutes to 98 ° C and fSrbt 60 minutes at boiling temperature. After After the liquor has cooled, the dyed knitted fabric is washed with water and dried, giving a streak-free, level, brilliant violet dyeing with good fastness properties.

Instead of the preparation according to Example 1, the aqueous preparations can also be used with similarly good results of Examples 2 to 18 can be used.

809815/0651

Claims (10)

27U316 Paten t ans nrU ehe 1. / Anionic araliphatic compounds, characterized in that that they are of the general formula I ² (1) RAO (-CH-CH-O) ---, CH ₂ -CH-CH ₂ -OX SO M OSO ₃ M correspond to where Λ a mono- or binuclear, aromatic residue, R alkyl with 4 to 22 carbon atoms, X alkyl with 1 to 18 carbon atoms} from Ζ, and Z _? one hydrogen and the other hydrogen or methyl, M a cation and η are 1 to 21. 2. Compounds according to claim 1, characterized in: that they correspond to the formula (1), wherein A is an optionally substituted benzene-diphenyl or means naphthalene radical. 3. Compounds according to any one of claims 1 and 2, characterized in that they correspond to formula (1), worir A denotes a benzene radical which is unsubstituted or substituted by hydroxyl, chlorine, methyl or methoxy. 809815/0651 ORIGINAL INSPECTED 4. Compounds according to any one of claims 1 to 3, characterized in that they correspond to formula (1) wherein M is hydrogen, an alkali or alkaline earth metal or an ammonium group, in particular hydrogen, an alkali metal or ammonium means. 5. Compounds according to one of claims 1 to 4, characterized in that they correspond to the formula (1) in which Z denotes hydrogen and Z "denotes hydrogen or methyl. 6. Compounds according to any one of claims 1 to 5, characterized in that they corresponded to formula (1), wherein η is 1 to 6, or preferably 1 to 3. 7. Compounds according to any one of claims 1 to 6, characterized marked that they are of the general formula Z ₁ Z I ¹ I ² (2) R ₁ - <j VOCCH-CH-OV- ^ Ch ₉ -CH-CH ₉ -OX ₁ ^r OSO ₃ M ₁ correspond to where R, alkyl with 4 to 18 carbon atoms, preferably 9 to 12 carbon atoms, of Z, and Z "one hydrogen and the other hydrogen or methyl, preferably both hydrogen, X, alkyl having 1 to 8 carbon atoms, preferably 4 to 8 carbon atoms, Μ, hydrogen, alkali metal or an ammouium group and n is 1 to 6, preferably 1 to 3. 809815/0661 8. Compounds according to any one of claims; 1 to 7, characterized by being of the general formula correspond to where R ₂ alkyl of 9 to 12 carbon atoms X ₂ alkyl of 4 to 8 carbon atoms M ~ hydrogen, alkali metal or ammonium and n _{n is} 1 to 3, preferably 1. 9. Process for the preparation of anionic araliphatic Compounds of the formula (1) given in claim 1, characterized in that one araliphatic compound the general formula RA-Oi CH-CH-OV ^ CH "-CH-CH _o -0-X II n-1 2 ι 2
Z ₁ Z ₂ OH in which A, R, X, Z ,, Z _n and η have the meaning given in claim 1, treated with a sulfonating agent and, if necessary, converted into a salt of the sulfonation product. 10. Use of anionic araliphatic compounds, the formula given in one of claims 1 to 8 as a dyeing aid in dyeing or printing. synthetic Polyamide fiber material with anionic dyes. 809815/0651